Tetrahydrofuranꢀ3ꢀols from epoxy alcohols
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 7, July, 2006
1303
colorless oils. The yield was 0.213 g (62% with respect to 1e).
Found (%): C, 70.00; H, 11.70. C10H20O2. Calculated (%):
C, 69.72; H, 11.70.
3. R. C. Larock, Comprehensive Organic Transformations.
A Guide to Functional Group Preparations, Wiley, Inc.,
1999, p. 905.
Major diastereomer. 1H NMR (CDCl3), δ: 0.85 (t, 3 H, J =
6.9 Hz); 1.20—1.74 (m, 11 H); 2.30 (quint, 1 H, J = 6.6 Hz);
2.43 (br.s, 1 H); 3.65 (m, 1 H); 3.71—3.82 (m, 2 H); 4.40
(m, 1 H). 13C NMR (CDCl3), δ: 14.0, 22.5, 26.2, 29.2, 31.7,
36.1, 41.4, 72.3, 75.2, 79.2.
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Minor diastereomer. 1H NMR (CDCl3), δ: 0.85 (t, 3 H, J =
6.9 Hz); 1.20—1.74 (m, 11 H); 1.95 (dd, 1 H, J = 13.2 Hz, J =
5.6 Hz); 2.43 (br.s, 1 H); 3.64 (dd, 1 H, J = 9.8 Hz, J = 4.4 Hz);
3.96 (dd, 1 H, J = 9.8 Hz, J = 4.7 Hz); 4.07, 4.44 (both m,
1 H each). 13C NMR (CDCl3), δ: 14.0, 22.5, 26.1, 29.3, 31.7,
35.4, 41.6, 72.4, 75.1, 78.1.
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4ꢀPhenylbutaneꢀ1,2,4ꢀtriol (4a). An aqueous 50% solution
of HClO4 (0.45 mL) was added to a solution of epoxy alcohol 2a
(0.255 g) in THF (1.25 mL) and water (2.5 mL). The mixture
was stirred at 20 °C for 18—20 h and neutralized with NaHCO3.
Impurities were extracted with CH2Cl2 and the aqueous layer
was largely concentrated in vacuo. The residue was mixed with
MeOH (5 mL) and CHCl3 (5 mL) was added. The inorganic
precipitate was filtered off and the filtrate was concentrated
in vacuo. A viscous oily residue mainly consisted of a 3 : 2
1
mixture of the diastereomers of triol 4a. H NMR (DMSOꢀd6),
δ: 1.43 (m, 0.6 H); 1.62—1.71 (m, 1.4 H); 3.19—3.40 (m, 2.4 H);
3.69 (m, 0.6 H); 4.50 (m, 1.6 H); 4.60 (br.s, 0.4 H); 4.68—4.78
(m, 1 H); 5.13 (br.s, 0.6 H); 5.21 (br.s, 0.4 H); 7.21 (m, 1 H);
7.26—7.38 (m, 4 H) (cf. Ref. 19).
5ꢀPhenyltetrahydrofuranꢀ3ꢀone (5a). Pyridinium chloroꢀ
chromate (604 mg, 2.8 mmol) was added to a solution of a
diastereomeric mixture of 3ꢀhydroxyꢀ5ꢀphenyltetrahydrofuran
(3a) (328 mg, 2 mmol) in CH2Cl2 (20 mL). The mixture was
stirred at 20 °C for 2—3 h (TLC monitoring), diluted with ether
(40 mL), and allowed to stand for 30 min. The mixture was
filtered through a column of neutral alumina and then the sorꢀ
bent was washed with ether—CH2Cl2 (1 : 1). The filtrate was
concentrated in vacuo and the residue was purified by column
chromatography in AcOEt—hexane with a concentration gradiꢀ
ent of AcOEt from 0 to 10%. The yield of ketone 5a was 195 mg
(60%). 1H NMR (DMSOꢀd6), δ: 2.51 (dd, 1 H, J = 17.8 Hz, J =
9.9 Hz); 2.88 (dd, 1 H, J = 17.8 Hz, J = 6.0 Hz); 3.98, 4.18
(both d, 1 H each, J = 16.7 Hz); 5.27 (dd, 1 H, J = 9.9 Hz, J =
6.0 Hz); 7.33 (t, 1 H, J = 7.0 Hz); 7.39 (t, 2 H, J = 7.0 Hz); 7.43
(d, 2 H, J = 7.3 Hz) (cf. Ref. 8c).
5ꢀMethylꢀ5ꢀphenyltetrahydrofuranꢀ3ꢀone (5b) was obtained
analogously. The yield was 73%, m.p. 51—52 °C. Found (%):
C, 75.29; H, 7.02. C11H12O2. Calculated (%): C, 74.98; H, 6.86.
1H NMR (CDCl3), δ: 1.68 (s, 3 H); 2.70, 2.92 (both d, 1 H each,
J = 17.6 Hz); 3.97, 4.14 (both d, 1 H each, J = 17.1 Hz); 7.28 (t,
1 H, J = 6.9 Hz); 7.34—7.42 (m, 4 H). 13C NMR (CDCl3), δ:
30.1, 49.9, 70.3, 83.7, 124.7, 127.4, 128.6, 144.5, 214.6.
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References
1. A. A. Semenov, Ocherk khimii prirodnykh soedinenii [An Outꢀ
line of the Chemistry of Natural Compounds], Nauka,
Novosibirsk, 2000, 298 pp. (in Russian).
2. M. D. Mashkovskii, Lekarstvennye sredstva [Drugs],
OOO "Izdatel´stvo Novaya Volna", Moscow, 2001, 1, 2 (in
Russian).
Received March 25, 2006;
in revised form July 26, 2006